Aqueous based blend composition and method of producing the same

ABSTRACT

An aqueous based blend composition including (a) an aqueous polyolefin dispersion comprising the melt blending product of one or more base polymers and one or more stabilizing agents in the presence of water and optionally one or more neutralizing agents, having an average volume particle size diameter from 400 to 1500 nm, and a pH from 8 to 11; and (b) from 0.1 to 50 percent by weight based on the solid content of the dispersion one or more crosslinking agents is provided.

The present application claims the benefit of PCT Application No.PCT/US2013/041320, filed on May 16, 2013; which claims priority to U.S.Provisional Application No. 61/661,389, filed on Jun. 19, 2012; thereferences which are incorporated herein.

FIELD OF INVENTION

The instant invention relates to an aqueous based blend composition andmethod of producing the same.

BACKGROUND OF THE INVENTION

The application of various treatment and pretreatment solutions to metalsubstrates to retard or inhibit corrosion is well known. This isparticularly true in the area of metal food and/or beverage containers,e.g. cans, as well as non-food metal containers. Coatings are typicallyapplied to the interior surface of such containers to prevent thecontents from contacting the metal parts of the container. Contactbetween the metal surface and the food and/or beverage as well asnon-food substances can lead to corrosion of the metal container, whichcan then contaminate the contents thereof. Corrosion is particularlyproblematic when food and/or beverage products are highly acidic innature or contain a high salt content such as a rhubarb-based productsor isotonic drinks. Highly alkaline contents of non-food substances suchas hair-dye may also react with metal, for example, aluminum, parts ofcontainers. The coatings applied, for example, to the interior of foodand/or beverage cans also help prevent corrosion in the head space ofthe cans, the area between the fill line of the food product and the canlid. The coatings may be applied to the outside of metal containers toprovide protection against the external environment and/or to provide adecorative layer including fillers and/or pigments. In addition tocorrosion protection, coatings for food and/or beverage cans should benon-toxic and inert, and, if applied to the internal surface, should notadversely affect the taste or appearance, e.g. color, of the food and/orbeverage in the can or contribute to a contamination of such contents.Resistance to “popping”, “blushing” and/or “blistering” is also desired.Certain coatings are particularly applicable for application onto coiledmetal stock, such as the coiled metal stock from which the ends of cansare made, “can end stock” and valve cups, e.g. top ends of aerosol cans.Since coatings designed for use on can end stock are applied prior tothe ends being cut and stamped out of the coiled metal stock, they arealso typically flexible and/or extensible. Such can end stock istypically coated on both sides. Thereafter, the coated metal stock ispunched and may be beaded or bent. It may also be scored for the“pop-top” opening and the pop-top ring is then attached with a pin thatis separately fabricated. The end is then attached to the can body by anedge rolling process. Accordingly, the coating applied to the can endstock typically has a certain degree of toughness and flexibility, suchthat it can withstand extensive fabrication processes, in addition tosome or all of the other desirable features discussed above. Variouscoatings such as epoxy-based and polyvinyl chloride-based, e.g.organosol type, coatings have been used in the past to coat the interiorof metal cans to prevent corrosion. However, there is a need for foodand/or beverage can liners as well as non-food container liners that canprovide improved properties such as having resistance to degradation incorrosive media as well as appropriate level of flexibility.

SUMMARY OF THE INVENTION

The instant invention is an aqueous based blend composition and methodof producing the same.

In one embodiment, the instant invention provides an aqueous based blendcomposition comprising: (a) an aqueous polyolefin dispersion comprisingthe melt blending product of one or more base polymers and one or morestabilizing agents in the presence of water and optionally one or moreneutralizing agents, wherein the polyolefin dispersion has an averagevolume particle size diameter in the range of from 400 to 1500 nm, and apH range from 8 to 11; and (b) one or more crosslinking agents selectedfrom the group consisting of phenol-formaldehyde resins,hydroxyalkylamide resins, amino-formaldehyde resins; epoxy groupcontaining resins, and combinations thereof, wherein said crosslinkingagents comprise form 0.1 to 50 percent by weight based on the solidcontent of the dispersion; wherein said aqueous based blend compositionhas a solid content in the range of from 15 to 70 percent by weight ofsolids, based on the weight of the aqueous based blend composition,wherein said solid content of said blend composition comprises up to99.9 percent by weight of the one or more base polymers, based on theweight of the solid content of the aqueous based blend composition,based on the weight of the solid content of the aqueous based blendcomposition, and a pH in the range of from 8 to 11.

In an alternative embodiment, the instant invention further provides aprocess for producing an aqueous based blend composition comprising: (1)selecting an aqueous polyolefin dispersion comprising the melt blendingproduct of one or more base polymers and one or more stabilizing agentsin the presence of water and optionally one or more neutralizing agents,wherein the polyolefin dispersion has an average volume particle sizediameter in the range of from 400 to 1500 nm, and a pH range from 8 to11; and (2) selecting one or more crosslinking agents selected from thegroup consisting of phenol-formaldehyde resins, hydroxyalkylamideresins, amino-formaldehyde resins; epoxy group containing resins, andcombinations thereof; and (3) contacting said aqueous polyolefindispersion and said one or more crosslinking agents to produce saidaqueous based blend composition; wherein said aqueous based blendcomposition has a solid content in the range of from 15 to 70 percent byweight of solids, based on the weight of the aqueous based blendcomposition, wherein said solid content of said blend compositioncomprises up to 99.1 percent by weight of the one or more base polymers,based on the weight of the solid content of the aqueous based blendcomposition and from 0.1 to 50 percent by weight of the one or morecrosslinking agents, based on the weight of the solid content of theaqueous based blend composition, and a pH in the range of from 8 to 11.

DETAILED DESCRIPTION OF THE INVENTION

The instant invention is an aqueous based blend composition and methodof producing the same.

In one embodiment, the instant invention provides an aqueous based blendcomposition comprising: (a) an aqueous polyolefin dispersion comprisingthe melt blending product of one or more base polymers and one or morestabilizing agents in the presence of water and optionally one or moreneutralizing agents, wherein the polyolefin dispersion has an averagevolume particle size diameter in the range of from 400 to 1500 nm, and apH range from 8 to 11; and (b) one or more crosslinking agents selectedfrom the group consisting of phenol-formaldehyde resins,hydroxyalkylamide resins, amino-formaldehyde resins; epoxy groupcontaining resins, and combinations thereof, wherein said crosslinkingagents comprise form 0.1 to 50 percent by weight based on the solidcontent of the dispersion; wherein said aqueous based blend compositionhas a solid content in the range of from 15 to 70 percent by weight ofsolids, based on the weight of the aqueous based blend composition,wherein said solid content of said blend composition comprises up to99.9 percent by weight of the one or more base polymers, based on theweight of the solid content of the aqueous based blend composition,based on the weight of the solid content of the aqueous based blendcomposition, and a pH in the range of from 8 to 11.

In an alternative embodiment, the instant invention further provides aprocess for producing an aqueous based blend composition comprising: (1)selecting an aqueous polyolefin dispersion comprising the melt blendingproduct of one or more base polymers and one or more stabilizing agentsin the presence of water and optionally one or more neutralizing agents,wherein the polyolefin dispersion has an average volume particle sizediameter in the range of from 400 to 1500 nm, and a pH range from 8 to11; and (2) selecting one or more crosslinking agents selected from thegroup consisting of phenol-formaldehyde resins, hydroxyalkylamideresins, amino-formaldehyde resins; epoxy group containing resins, andcombinations thereof; and (3) contacting said aqueous polyolefindispersion and said one or more crosslinking agents to produce saidaqueous based blend composition; wherein said aqueous based blendcomposition has a solid content in the range of from 15 to 70 percent byweight of solids, based on the weight of the aqueous based blendcomposition, wherein said solid content of said blend compositioncomprises up to 99.1 percent by weight of the one or more base polymers,based on the weight of the solid content of the aqueous based blendcomposition and from 0.1 to 50 percent by weight of the one or morecrosslinking agents, based on the weight of the solid content of theaqueous based blend composition, and a pH in the range of from 8 to 11.

Aqueous Polyolefin Dispersion Component

The aqueous polyolefin dispersion component of the present inventioncomprises the melt blending product of one or more base polymers and oneor more stabilizing agents in the presence of water and optionally oneor more neutralizing agents, wherein the polyolefin dispersion has anaverage volume particle size diameter in the range of from 400 to 1500nm; a pH range from 8 to 11, a solid content in the range of from 25 to75, e.g. from 35 to 65, weight percent, based on the weight of thedispersion.

Base Polymer

The aqueous polyolefin dispersion comprises from up to 99.9 percent byweight of one or more base polymers, based on the total weight of thesolid content of the aqueous dispersion. All individual values andsubranges up to 99.9 weight percent are included herein and disclosedherein; for example, the weight percent can be from a lower limit of 25,30, 35, or 45 weight percent to an upper limit of 50, 55, 60, 65, 70,75, 85, 90, or 95 weight percent. For example, the aqueous dispersionmay comprise from 25 to 95, or from 35 to 95, or 35 to 85, or from 45 to95 percent by weight of one or more base polymers, based on the totalweight of the solid content of the aqueous dispersion. The aqueousdispersion comprises at least one or more base polymers. The basepolymer may, for example, be a thermoplastic material. The one or morebase polymers may comprise one or more olefin based polymers.

Examples of thermoplastic materials include, but are not limited to,homopolymers and copolymers (including elastomers) of one or morealpha-olefins such as ethylene, propylene, 1-butene, 3-methyl-1-butene,4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1-hexene, 1-octene,1-decene, and 1-dodecene, as typically represented by polyethylene,polypropylene, poly-1-butene, poly-3-methyl-1-butene,poly-3-methyl-1-pentene, poly-4-methyl-1-pentene, ethylene-propylenecopolymer, ethylene-1-butene copolymer, and propylene-1-butenecopolymer; copolymers (including elastomers) of an alpha-olefin with aconjugated or non-conjugated diene, as typically represented byethylene-butadiene copolymer and ethylene-ethylidene norbornenecopolymer; and polyolefins (including elastomers) such as copolymers oftwo or more alpha-olefins with a conjugated or non-conjugated diene, astypically represented by ethylene-propylene-butadiene copolymer,ethylene-propylene-dicyclopentadiene copolymer,ethylene-propylene-1,5-hexadiene copolymer, andethylene-propylene-ethylidene norbornene copolymer; ethylene-vinylcompound copolymers such as ethylene-vinyl acetate copolymer,ethylene-vinyl alcohol copolymer, ethylene-vinyl chloride copolymer,ethylene acrylic acid or ethylene-(meth)acrylic acid copolymers, andethylene-(meth)acrylate copolymer; styrenic copolymers (includingelastomers) such as polystyrene, ABS, acrylonitrile-styrene copolymer,α-methylstyrene-styrene copolymer, styrene vinyl alcohol, styreneacrylates such as styrene methylacrylate, styrene butyl acrylate,styrene butyl methacrylate, and styrene butadienes and crosslinkedstyrene polymers; and styrene block copolymers (including elastomers)such as styrene-butadiene copolymer and hydrate thereof, andstyrene-isoprene-styrene triblock copolymer; polyvinyl compounds such aspolyvinyl chloride, polyvinylidene chloride, vinyl chloride-vinylidenechloride copolymer, polymethyl acrylate, and polymethyl methacrylate;polyamides such as nylon 6, nylon 6,6, and nylon 12; thermoplasticpolyesters such as polyethylene terephthalate and polybutyleneterephthalate; polycarbonate, polyphenylene oxide, and the like; andglassy hydrocarbon-based resins, including poly-dicyclopentadienepolymers and related polymers (copolymers, terpolymers); saturatedmono-olefins such as vinyl acetate, vinyl propionate, vinyl versatate,and vinyl butyrate and the like; vinyl esters such as esters ofmonocarboxylic acids, including methyl acrylate, ethyl acrylate, n-butylacrylate, isobutyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate,n-octyl acrylate, phenyl acrylate, methyl methacrylate, ethylmethacrylate, and butyl methacrylate and the like; acrylonitrile,methacrylonitrile, acrylamide, mixtures thereof; resins produced by ringopening metathesis and cross metathesis polymerization and the like.These resins may be used either alone or in combinations of two or more.

Exemplary (meth)acrylates, as base polymers, include, but are notlimited to, methyl acrylate, ethyl acrylate, butyl acrylate, hexylacrylate, 2-ethylhexyl acrylate, octyl acrylate and isooctyl acrylate,n-decyl acrylate, isodecyl acrylate, tert-butyl acrylate, methylmethacrylate, butyl methacrylate, hexyl methacrylate, isobutylmethacrylate, isopropyl methacrylate as well as 2-hydroxyethyl acrylateand acrylamide. The preferred (meth)acrylates are methyl acrylate, ethylacrylate, butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate,isooctyl acrylate, methyl methacrylate and butyl methacrylate. Othersuitable (meth)acrylates that can be polymerized from monomers includelower alkyl acrylates and methacrylates including acrylic andmethacrylic ester monomers: methyl acrylate, ethyl acrylate, n-butylacrylate, t-butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate,isobornyl acrylate, methyl methacrylate, ethyl methacrylate, n-propylmethacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutylmethacrylate, sec-butyl methacrylate, cyclohexyl methacrylate, isodecylmethacrylate, isobornyl methacrylate, t-butylaminoethyl methacrylate,stearyl methacrylate, glycidyl methacrylate, dicyclopentenylmethacrylate, phenyl methacrylate.

In selected embodiments, base polymer may, for example, comprise one ormore polyolefins selected from the group consisting of ethylene-alphaolefin copolymers, propylene-alpha olefin copolymers, and olefin blockcopolymers. In particular, in select embodiments, the base polymer maycomprise one or more non-polar polyolefins.

In specific embodiments, polyolefins such as polypropylene,polyethylene, copolymers thereof, and blends thereof, as well asethylene-propylene-diene terpolymers, may be used. In some embodiments,exemplary olefinic polymers include homogeneous polymers, as describedin U.S. Pat. No. 3,645,992; high density polyethylene (HDPE), asdescribed in U.S. Pat. No. 4,076,698; heterogeneously branched linearlow density polyethylene (LLDPE); heterogeneously branched ultra lowlinear density polyethylene (ULDPE); homogeneously branched, linearethylene/alpha-olefin copolymers; homogeneously branched, substantiallylinear ethylene/alpha-olefin polymers, which can be prepared, forexample, by processes disclosed in U.S. Pat. Nos. 5,272,236 and5,278,272, the disclosures of which are incorporated herein byreference; and high pressure, free radical polymerized ethylene polymersand copolymers such as low density polyethylene (LDPE) or ethylene vinylacetate polymers (EVA).

In other particular embodiments, the base polymer may, for example, beethylene vinyl acetate (EVA) based polymers. In other embodiments, thebase polymer may, for example, be ethylene-methyl acrylate (EMA) basedpolymers. In other particular embodiments, the ethylene-alpha olefincopolymer may, for example, be ethylene-butene, ethylene-hexene, orethylene-octene copolymers or interpolymers. In other particularembodiments, the propylene-alpha olefin copolymer may, for example, be apropylene-ethylene or a propylene-ethylene-butene copolymer orinterpolymer.

In one embodiment, the base polymer may be a conventional polypropylenesuch as propylene homopolymer and/or a random propylene copolymer (RCP).The propylene homopolymer can have a melt flow rate in the range of from1 to 100 g/10 minutes and a DSC melting point of 140° C. to 170° C. TheRCP can have a DSC melting point in the range of from 120° C. to 160°C., for example, from 130° C. to 160° C., or from 141° C. to 159° C.,and a melt flow rate (MFR) in the range of from 1 to 120 g/10 minutes,for example, from 5 to 120 g/10 minutes, or from 11 to 99 g/10 minutes,or from 19 to 84 g/10 minutes, measured according to ASTM-D 1238, (230°C./2.16 kg). Such RCP materials are commercially available under varioustrade names from Braskem America Inc. or Formosa Plastics Corporation,USA.

In certain other embodiments, the base polymer may, for example, be asemi-crystalline polymer and may have a melting point of less than 110°C. In another embodiment, the melting point may be from 25 to 100° C. Inanother embodiment, the melting point may be between 40 and 85° C.

In one particular embodiment, the base polymer is apropylene/alpha-olefin copolymer, which is characterized as havingsubstantially isotactic propylene sequences. “Substantially isotacticpropylene sequences” means that the sequences have an isotactic triad(mm) measured by ¹³C NMR of greater than about 0.85; in the alternative,greater than about 0.90; in another alternative, greater than about0.92; and in another alternative, greater than about 0.93. Isotactictriads are well-known in the art and are described in, for example, U.S.Pat. No. 5,504,172 and International Publication No. WO 00/01745, whichrefer to the isotactic sequence in terms of a triad unit in thecopolymer molecular chain determined by ¹³C NMR spectra.

The propylene/alpha-olefin copolymer may have a melt flow rate in therange of from 0.1 to 25 g/10 minutes, measured in accordance with ASTMD-1238 (at 230° C./2.16 Kg). All individual values and subranges from0.1 to 25 g/10 minutes are included herein and disclosed herein; forexample, the melt flow rate can be from a lower limit of 0.1 g/10minutes, 0.2 g/10 minutes, 0.5 g/10 minutes, 2 g/10 minutes, 4 g/10minutes, 5 g/10 minutes, 10 g/10 minutes, or 15 g/10 minutes to an upperlimit of 25 g/10 minutes, 20 g/10 minutes, 18 g/10 minutes, 15 g/10minutes, 10 g/10 minutes, 8 g/10 minutes, or 5 g/10 minutes. Forexample, the propylene/alpha-olefin copolymer may have a melt flow ratein the range of from 0.1 to 20 g/10 minutes; or from 0.1 to 18 g/10minutes; or from 0.1 to 15 g/10 minutes; or from 0.1 to 12 g/10 minutes;or from 0.1 to 10 g/10 minutes; or from 0.1 to 5 g/10 minutes.

The propylene/alpha-olefin copolymer has a crystallinity in the range offrom at least 1 percent by weight (a heat of fusion of at least 2Joules/gram) to 30 percent by weight (a heat of fusion of less than 50Joules/gram). All individual values and subranges from 1 percent byweight (a heat of fusion of at least 2 Joules/gram) to 30 percent byweight (a heat of fusion of less than 50 Joules/gram) are includedherein and disclosed herein; for example, the crystallinity can be froma lower limit of 1 percent by weight (a heat of fusion of at least 2Joules/gram), 2.5 percent (a heat of fusion of at least 4 Joules/gram),or 3 percent (a heat of fusion of at least 5 Joules/gram) to an upperlimit of 30 percent by weight (a heat of fusion of less than 50Joules/gram), 24 percent by weight (a heat of fusion of less than 40Joules/gram), 15 percent by weight (a heat of fusion of less than 24.8Joules/gram) or 7 percent by weight (a heat of fusion of less than 11Joules/gram). For example, the propylene/alpha-olefin copolymer may havea crystallinity in the range of from at least 1 percent by weight (aheat of fusion of at least 2 Joules/gram) to 24 percent by weight (aheat of fusion of less than 40 Joules/gram); or in the alternative, thepropylene/alpha-olefin copolymer may have a crystallinity in the rangeof from at least 1 percent by weight (a heat of fusion of at least 2Joules/gram) to 15 percent by weight (a heat of fusion of less than 24.8Joules/gram); or in the alternative, the propylene/alpha-olefincopolymer may have a crystallinity in the range of from at least 1percent by weight (a heat of fusion of at least 2 Joules/gram) to 7percent by weight (a heat of fusion of less than 11 Joules/gram); or inthe alternative, the propylene/alpha-olefin copolymer may have acrystallinity in the range of from at least 1 percent by weight (a heatof fusion of at least 2 Joules/gram) to 5 percent by weight (a heat offusion of less than 8.3 Joules/gram). The crystallinity is measured viaDifferential scanning calorimetry (DSC) method. Thepropylene/alpha-olefin copolymer comprises units derived from propyleneand polymeric units derived from one or more alpha-olefin comonomers.Exemplary comonomers utilized to manufacture the propylene/alpha-olefincopolymer are C₂, and C₄ to C₁₀ alpha-olefins; for example, C₂, C₄, C₆and C₈ alpha-olefins.

The propylene/alpha-olefin copolymer comprises from 1 to 40 percent byweight of units derived from one or more alpha-olefin comonomers. Allindividual values and subranges from 1 to 40 weight percent are includedherein and disclosed herein; for example, the weight percent of unitsderived from one or more alpha-olefin comonomers can be from a lowerlimit of 1, 3, 4, 5, 7, or 9 weight percent to an upper limit of 40, 35,30, 27, 20, 15, 12, or 9 weight percent. For example, thepropylene/alpha-olefin copolymer comprises from 1 to 35 percent byweight of units derived from one or more alpha-olefin comonomers; or inthe alternative, the propylene/alpha-olefin copolymer comprises from 1to 30 percent by weight of units derived from one or more alpha-olefincomonomers; or in the alternative, the propylene/alpha-olefin copolymercomprises from 3 to 27 percent by weight of units derived from one ormore alpha-olefin comonomers; or in the alternative, thepropylene/alpha-olefin copolymer comprises from 3 to 20 percent byweight of units derived from one or more alpha-olefin comonomers; or inthe alternative, the propylene/alpha-olefin copolymer comprises from 3to 15 percent by weight of units derived from one or more alpha-olefincomonomers.

The propylene/alpha-olefin copolymer has a molecular weight distribution(MWD), defined as weight average molecular weight divided by numberaverage molecular weight (M_(w)/M_(n)) of 3.5 or less; in thealternative 3.0 or less; or in another alternative from 1.8 to 3.0.

Such propylene/alpha-olefin copolymers are further described in detailsin the U.S. Pat. Nos. 6,960,635 and 6,525,157, incorporated herein byreference. Such propylene/alpha-olefin copolymers are commerciallyavailable from The Dow Chemical Company, under the tradename VERSIFY™,or from ExxonMobil Chemical Company, under the tradename VISTAMAXX™.

In one embodiment, the propylene/alpha-olefin copolymers are furthercharacterized as comprising (A) between 60 and less than 100, preferablybetween 80 and 99 and more preferably between 85 and 99, weight percentunits derived from propylene, and (B) between greater than zero and 40,preferably between 1 and 20, more preferably between 4 and 16 and evenmore preferably between 4 and 15, weight percent units derived from atleast one of ethylene and/or a C₄₋₁₀ α-olefin; and containing an averageof at least 0.001, preferably an average of at least 0.005 and morepreferably an average of at least 0.01, long chain branches/1000 totalcarbons, wherein the term long chain branch, as used herein, refers to achain length of at least one (1) carbon more than a short chain branch,and short chain branch, as used herein, refers to a chain length of two(2) carbons less than the number of carbons in the comonomer. Forexample, a propylene/1-octene interpolymer has backbones with long chainbranches of at least seven (7) carbons in length, but these backbonesalso have short chain branches of only six (6) carbons in length. Themaximum number of long chain branches typically it does not exceed 3long chain branches/1000 total carbons. Such propylene/alpha-olefincopolymers are further described in details in the U.S. ProvisionalPatent Application No. 60/988,999 and International Patent ApplicationNo. PCT/US08/082599, each of which is incorporated herein by reference.

In certain other embodiments, the base polymer, e.g.propylene/alpha-olefin copolymer, may, for example, be asemi-crystalline polymer and may have a melting point of less than 110°C. In preferred embodiments, the melting point may be from 25 to 100° C.In more preferred embodiments, the melting point may be between 40 and85° C.

In other selected embodiments, olefin block copolymers, e.g., ethylenemulti-block copolymer, such as those described in the InternationalPublication No. WO2005/090427 and U.S. Patent Application PublicationNo. US 2006/0199930, incorporated herein by reference to the extentdescribing such olefin block copolymers, may be used as the basepolymer. Such olefin block copolymer may be an ethylene/α-olefininterpolymer:

(a) having a M_(w)/M_(n) from about 1.7 to about 3.5, at least onemelting point, T_(m), in degrees Celsius, and a density, d, ingrams/cubic centimeter, wherein the numerical values of T_(m), and dcorresponding to the relationship:T _(m)>−2002.9+4538.5(d)−2422.2(d)²; or

(b) having a M_(w)/M_(n) from about 1.7 to about 3.5, and beingcharacterized by a heat of fusion, ΔH in J/g, and a delta quantity, ΔT,in degrees Celsius defined as the temperature difference between thetallest DSC peak and the tallest CRYSTAF peak, wherein the numericalvalues of ΔT and ΔH having the following relationships:ΔT>−0.1299(ΔH)+62.81 for ΔH greater than zero and up to 130 J/g,ΔT≥48° C. for ΔH greater than 130 J/g,

wherein the CRYSTAF peak being determined using at least 5 percent ofthe cumulative polymer, and if less than 5 percent of the polymer havingan identifiable CRYSTAF peak, then the CRYSTAF temperature being 30° C.;or

(c) being characterized by an elastic recovery, Re, in percent at 300percent strain and 1 cycle measured with a compression-molded film ofthe ethylene/α-olefin interpolymer, and having a density, d, ingrams/cubic centimeter, wherein the numerical values of Re and dsatisfying the following relationship when ethylene/α-olefininterpolymer being substantially free of a cross-linked phase:Re>1481-1629(d); or

(d) having a molecular fraction which elutes between 40° C. and 130° C.when fractionated using TREF, characterized in that the fraction havinga molar comonomer content of at least 5 percent higher than that of acomparable random ethylene interpolymer fraction eluting between thesame temperatures, wherein said comparable random ethylene interpolymerhaving the same comonomer(s) and having a melt index, density, and molarcomonomer content (based on the whole polymer) within 10 percent of thatof the ethylene/α-olefin interpolymer; or

(e) having a storage modulus at 25° C., G′ (25° C.), and a storagemodulus at 100° C., G′ (100° C.), wherein the ratio of G′ (25° C.) to G′(100° C.) being in the range of about 1:1 to about 9:1.

Such olefin block copolymer, e.g. ethylene/α-olefin interpolymer mayalso:

(a) have a molecular fraction which elutes between 40° C. and 130° C.when fractionated using TREF, characterized in that the fraction havinga block index of at least 0.5 and up to about 1 and a molecular weightdistribution, M_(w)/M_(n), greater than about 1.3; or

(b) have an average block index greater than zero and up to about 1.0and a molecular weight distribution, M_(w)/M_(n), greater than about1.3.

In certain embodiments, the base polymer may, for example, comprise apolar polymer, having a polar group as either a comonomer or graftedmonomer. In exemplary embodiments, the base polymer may, for example,comprise one or more polar polyolefins, having a polar group as either acomonomer or grafted monomer. Exemplary polar polyolefins include, butare not limited to, ethylene-acrylic acid (EAA) and ethylene-methacrylicacid copolymers, such as those available under the trademarks PRIMACOR™,commercially available from The Dow Chemical Company, NUCREL™,commercially available from E.I. DuPont de Nemours, and ESCOR™,commercially available from ExxonMobil Chemical Company and described inU.S. Pat. Nos. 4,599,392, 4,988,781, and 5,938,437, each of which isincorporated herein by reference in its entirety. Other exemplary basepolymers include, but are not limited to, ethylene ethyl acrylate (EEA)copolymer, ethylene methyl methacrylate (EMMA), and ethylene butylacrylate (EBA).

In one embodiment, the base polymer may, for example, comprise a polarpolyolefin selected from the group consisting of ethylene-acrylic acid(EAA) copolymer, ethylene-methacrylic acid copolymer, and combinationsthereof, and the stabilizing agent may, for example, comprise a polarpolyolefin selected from the group consisting of ethylene-acrylic acid(EAA) copolymer, ethylene-methacrylic acid copolymer, and combinationsthereof; provided, however, that base polymer may, for example, have alower acid number, measured according to ASTM D-974, than thestabilizing agent.

Those having ordinary skill in the art will recognize that the abovelist is a non-comprehensive listing of exemplary base polymers. It willbe appreciated that the scope of the present invention is restricted bythe claims only.

Stabilizing Agent

The dispersion according to the present invention may further compriseat least one or more stabilizing agents, also referred to herein asdispersion agents, to promote the formation of a stable dispersion. Thestabilizing agent may preferably be an external stabilizing agent. Thedispersion of the instant invention comprises 1 to 50 percent by weightof one or more stabilizing agents, based on the total weight of thesolid content of the dispersion. All individual values and subrangesfrom 1 to 50 weight percent are included herein and disclosed herein;for example, the weight percent can be from a lower limit of 1, 3, 5, 10weight percent to an upper limit of 15, 25, 35, 45, or 50 weightpercent. For example, the dispersion may comprise from 1 to 25, or inthe alternative from 1 to 35, or in the alternative from 1 to 40, or inthe alternative from 1 to 50 percent by weight of one or morestabilizing agents, based on the total weight of the solid content ofthe dispersion. In selected embodiments, the stabilizing agent may be asurfactant, a polymer, or mixtures thereof. In certain embodiments, thestabilizing agent can be a polar polymer, having a polar group as eithera comonomer or grafted monomer. In exemplary embodiments, thestabilizing agent comprises one or more polar polyolefins, having apolar group as either a comonomer or grafted monomer. Exemplarypolymeric stabilizing agents include, but are not limited to,ethylene-acrylic acid (EAA) and ethylene-methacrylic acid copolymers,such as those available under the trademarks PRIMACOR™, commerciallyavailable from The Dow Chemical Company, NUCREL™, commercially availablefrom E.I. DuPont de Nemours, and ESCOR™ commercially available fromExxonMobil Chemical Company and described in U.S. Pat. Nos. 4,599,392,4,988,781, and 5,938,437, each of which is incorporated herein byreference in its entirety. Other exemplary polymeric stabilizing agentsinclude, but are not limited to, ethylene ethyl acrylate (EEA)copolymer, ethylene methyl methacrylate (EMMA), and ethylene butylacrylate (EBA). Other ethylene-carboxylic acid copolymer may also beused. Those having ordinary skill in the art will recognize that anumber of other useful polymers may also be used. Such polymers arecommercially available, for example, under the trade names LICOCENE fromClariant Corporation, EXXELOR from ExxonMobil Chemical Company, orEpolene from Westlake Chemical Company.

Other stabilizing agents that may be used include, but are not limitedto, long chain fatty acids, fatty acid salts, or fatty acid alkyl estershaving from 12 to 60 carbon atoms. In other embodiments, the long chainfatty acid or fatty acid salt may have from 12 to 40 carbon atoms.

The stabilizing agent may be partially or fully neutralized with aneutralizing agent. In certain embodiments, neutralization of thestabilizing agent, such as a long chain fatty acid or EAA, may be from25 to 200 percent on a molar basis; or in the alternative, it may befrom 50 to 110 percent on a molar basis. For example, for EAA, theneutralizing agent may be a base, such as ammonium hydroxide orpotassium hydroxide, for example. Other neutralizing agents can includelithium hydroxide or sodium hydroxide, for example. In anotheralternative, the neutralizing agent may, for example, be a carbonate. Inanother alternative, the neutralizing agent may, for example, be anyamine such as monoethanolamine, or 2-amino-2-methyl-1-propanol (AMP)Amines useful in embodiments disclosed herein may includemonoethanolamine, diethanolamine, triethanolamine, and TRIS AMINO (eachavailable from Angus), NEUTROL TE (available from BASF), as well astriisopropanolamine, diisopropanolamine, and N,N-dimethylethanolamine(each available from The Dow Chemical Company, Midland, Mich.). Otheruseful amines may include ammonia, monomethylamine, dimethylamine,trimethylamine, monoethylamine, diethylamine, triethylamine,mono-n-propylamine, dimethyl-n propylamine, N-methanol amine,N-aminoethylethanolamine, N-methyldiethanolamine, monoisopropanolamine,N,N-dimethyl propanolamine, 2-amino-2-methyl-1-propanol,tris(hydroxymethyl)-aminomethane, N,N,N′N′-tetrakis(2-hydroxylpropyl)ethylenediamine, 1.2-diaminopropane. In some embodiments, mixtures ofamines or mixtures of amines and surfactants may be used. Those havingordinary skill in the art will appreciate that the selection of anappropriate neutralizing agent depends on the specific compositionformulated, and that such a choice is within the knowledge of those ofordinary skill in the art.

Additional stabilizing agents that may be useful in the practice of thepresent invention include, but are not limited to, cationic surfactants,anionic surfactants, or non-ionic surfactants. Examples of anionicsurfactants include, but are not limited to, sulfonates, carboxylates,and phosphates. Examples of cationic surfactants include, but are notlimited to, quaternary amines Examples of non-ionic surfactants include,but are not limited to, block copolymers containing ethylene oxide andsilicone surfactants. Stabilizing agents useful in the practice of thepresent invention can be either external surfactants or internalsurfactants. External surfactants are surfactants that do not becomechemically reacted into the base polymer during dispersion preparation.Examples of external surfactants useful herein include, but are notlimited to, salts of dodecyl benzene sulfonic acid and lauryl sulfonicacid salt. Internal surfactants are surfactants that do becomechemically reacted into the base polymer during dispersion preparation.An example of an internal surfactant useful herein includes2,2-dimethylol propionic acid and its salts. Additional surfactants thatmay be useful in the practice of the present invention include cationicsurfactants, anionic surfactants, non-ionic surfactants, or combinationsthereof. Various commercially available surfactants may be used inembodiments disclosed herein, including: OP-100 (a sodium stearate),OPK-1000 (a potassium stearate), and OPK-181 (a potassium oleate), eachavailable from RTD Hallstar; UNICID 350, available from Baker Petrolite;DISPONIL FES 77-IS and DISPONIL TA-430, each available from Cognis;RHODAPEX CO-436, SOPROPHOR 4D384, 3D-33, and 796/P, RHODACAL BX-78 andLDS-22, RHODAFAC RE-610, and RM-710, and SUPRAGIL MNS/90, each availablefrom Rhodia; and TRITON QS-15, TRITON W-30, DOWFAX 2A1, DOWFAX 3B2,DOWFAX 8390, DOWFAX C6L, TRITON X-200, TRITON XN-455, TRITON H-55,TRITON GR-5M, TRITON BG-10, and TRITON CG-110, each available from TheDow Chemical Company, Midland, Mich.

Fluid Medium

The dispersion further comprises a fluid medium. The fluid medium iswater. The dispersion of the instant invention comprises 35 to 85percent by weight of water; for example from 25 to 75 percent by weightof water, or in the alternative, from 40 to 60 percent by weight ofwater, or in the alternative, from 45 to 55 percent by weight of water,based on the weight of the dispersion. Water content of the dispersionmay preferably be controlled so that the solids content (base polymerplus stabilizing agent) is between about 25 percent to about 75 percentby weight, based on the weight of the dispersion.

Additional Components

The aqueous polyolefin dispersion according to the present invention mayfurther comprise optionally one or more co-solvents, e.g. glycols,glycol ether, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, alcohols,mineral spirits, and benzoate esters; optionally one or moredispersants, e.g. aminoalcohols, and polycarboxylates; optionally one ormore surfactants; optionally one or more antioxidants such as hinderedphenolic, e.g. PENTAERYTHRITOLTETRAKIS(3,5-DI-TERT-BUTYL-4-HYDROXYHYDROCINNAMATE), optionally one ormore lubricants, optionally one or more defoamers; optionally one ormore crosslinking agents; optionally one or more preservatives, e.g.biocides, mildewcides, fungicides, algaecides, and combinations thereof;optionally one or more thickeners, e.g. cellulosic based thickeners suchas hydroxyethyl cellulose, hydrophobically modified alkali solubleemulsions (HASE thickeners such as UCAR POLYPHOBE TR-116) andhydrophobically modified ethoxylated urethane thickeners (HEUR); oroptionally one or more additional neutralizing agents, e.g. hydroxides,amines, ammonia, and carbonates.

Forming the Aqueous Polyolefin Dispersion

The aqueous polyolefin dispersion can be formed by any number of methodsrecognized by those having skill in the art. In one embodiment, one ormore base polymers, one or more stabilizing agents are melt-kneaded inan extruder along with water and a neutralizing agent, such as ammonia,potassium hydroxide, or a combination of the two to form a dispersion.In some embodiments, the dispersion is first diluted to contain about 1to about 3% by weight water and then, subsequently, further diluted tocomprise greater than about 25% by weight water.

Any melt-kneading means known in the art may be used. In someembodiments, a kneader, a BANBURY® mixer, single-screw extruder, or amulti-screw extruder, e.g. a twin screw extruder, is used. A process forproducing the dispersions in accordance with the present invention isnot particularly limited. For example, an extruder, in certainembodiments, for example, a twin screw extruder, is coupled to a backpressure regulator, melt pump, or gear pump. Exemplary embodiments alsoprovide a base reservoir and an initial water reservoir, each of whichincludes a pump. Desired amounts of base and initial water are providedfrom the base reservoir and the initial water reservoir, respectively.Any suitable pump may be used, but in some embodiments, for example, apump that provides a flow of about 150 cc/min at a pressure of 240 baris used to provide the base and the initial water to the extruder. Inother embodiments, a liquid injection pump provides a flow of 300 cc/minat 200 bar or 600 cc/min at 133 bar. In some embodiments, the base andinitial water are preheated in a preheater.

One or more base polymers, in the form of pellets, powder, or flakes,are fed from the feeder to an inlet of the extruder where the resin ismelted. In some embodiments, the dispersing agent is added to one ormore base polymers through and along with the resin and in otherembodiments, the dispersing agent is provided separately to the twinscrew extruder. The resin melt is then delivered from the mix and conveyzone to an emulsification zone of the extruder where the initial amountof water and base from the water and base reservoirs are added throughan inlet. In some embodiments, dispersing agent may be addedadditionally or exclusively to the water stream. In some embodiments,further dilution water may be added via water inlet from water reservoirin a dilution and cooling zone of the extruder. Typically, thedispersion is diluted to at least 30 weight percent water in the coolingzone. In addition, the diluted mixture may be diluted any number oftimes until the desired dilution level is achieved. In some embodiments,water is not added into the twin screw extruder but rather to a streamcontaining the resin melt after the melt has exited from the extruder.In this manner, steam pressure build-up in the extruder is eliminatedand the dispersion is formed in a secondary mixing device such as arotor stator mixer.

In one embodiment, the process for producing the aqueous dispersioncomprises the steps of (1) selecting one or more base polymers; (2)selecting one or more stabilizing agents; (3) selecting a liquid mediacomprising water; (4) optionally selecting one or more neutralizingagents; (5) melt-blending the one or more base polymers and one or morestabilizing agents in the presence of water and optionally one or moreneutralizing agents; (6) thereby forming an emulsified mixture; (7)contacting said emulsified mixture with additional dilution water whileoptionally removing heat therefrom; (8) thereby forming solid particlesdispersed in said water; and (9) thereby forming said dispersion.

Crosslinking Agent

The aqueous base blend composition further comprises at least one ormore crosslinking agents to promote crosslinking. The aqueous base blendcomposition comprises 1 to 50 percent by weight of one or morecrosslinking agents, based on the total weight of the solid content ofthe dispersion. For example, the aqueous base blend compositioncomprises from 1 to 18; or in the alternative, from 1 to 15; or in thealternative, from 1 to 12; or in the alternative, from 1 to 10; or inthe alternative, from 1 to 20; or in the alternative, from 1 to 30; orin the alternative, from 1 to 40; or in the alternative, from 1 to 45;or in the alternative, from 1 to 50 percent by weight of one or morecrosslinking agents, based on the total weight of the solid content ofthe aqueous base blend composition. In selected embodiments thecrosslinking agent is phenol-formaldehyde resins; hydroxyalkylamideresins; amino-formaldehyde resins including, but not limited to,urea-formaldehyde resins, melamine formaldehyde resins, benzoguanamineformaldehyde resins, anhydride resins; epoxy group containing resins,including, but not limited, to epoxy resins, epoxy group containingpolyester or acrylic resins and blocked isocyanate resins, andcombinations of two or more thereof, provided that the combinations ofsuch crosslinkers is compatible.

Crosslinking agent may be a compound, which reacts with a reactivefunctional group contained in the aqueous base blend compositionformulation; thereby facilitating the crosslinking between suchfunctional groups. Such functional groups can be present in both thebase polymer as well as the stabilizing agent.

For example, reactive functional groups include, but are not limited to,acid groups such as carboxylic acid groups, free or in the neutralizedform, or any functional groups having another active hydrogen by anothercomponent such as alcohol groups, amino groups, epoxy groups, or thelike.

Crosslinkable functional groups in the cross-linking agent are groupscapable of reacting with the reactive functional group of the basepolymer and/or the stabilizer. For example, a carbodiimide group, anoxazoline group, an isocyanate group, a hydroxyalkylamide group, anepoxy group, a methylol group, an aldehyde group, an acid anhydridegroup, a hydroxy group, an aziridinyl group or a silane group can beused in a crosslinker.

Another possibility of crosslinking acid functional groups is by use ofmultivalent metal ions by reaction of the aforementioned acid groupswith a multivalent metal ion containing substance, such as zinc oxide.

Carboxylic acids could also be crosslinked in reactions withmultifunctional olefinic unsaturated substances under catalysis of astrong acid. Multifunctional carbonates could also react with carboxylicacids to give ester linkages with liberation of carbon dioxide.

In the alternative, polyolefinic materials may be crosslinked via freeradical crosslinking, initiated by addition of peroxides or viaradiation, e.g., electron beam.

With respect to crosslinkable functional groups, one or more may bepresent in a crosslinking agent. In the alternative, two or morecrosslinkable functional groups may be present in a single molecule.

The cross-linking agent having the above described crosslinkablefunctional group may be a waterdispersed or waterdispersible orwater-soluble substance. In one embodiment, exemplary crosslinkingagents include, but are not limited to, an aqueous monomeric orpolymeric substance, which contains two or more oxazoline groups,carbodiimide groups, hydroxyalkylamide groups, epoxy groups, isocyanategroups, methylol groups etc. or several of these per molecule.

An exemplary oxazoline crosslinking agent is an aqueous polymer havingtwo or more oxazoline groups in its molecules, substances can beobtained by polymerizing an oxazoline group-containing monomer and, asrequired, an ethylenic unsaturated monomer. Alternatively an oxazolinecrosslinking agent can also be obtained by reaction between a nitrilegroup and an aminoethanol group, dehydration of a hydroxylalkylamidegroup and the like.

Crosslinking agents having two or more carbodiimide groups can beproduced from diisocyanate compounds by a condensation reactionaccompanied by decarboxylation reaction of a diisocyanate compound.Examples of the diisocyanate compound include, but are not limited to,1,5-naphthylene diisocyanate, 4,4′-diphenylmethane diisocyanate,4,4′-diphenyldimethylmethane diisocyanate, 1,4-phenylene diisocyanate,2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexanemethylenediisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate,isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate,methylcyclohexane diisocyanate, and tetramethylxylylene diisocyanate andthe like. These compounds may also be used as mixtures.

Monofunctional isocyanates may be included to control the resinmolecular chain length such as phenyl isocyanate, tolyl isocyanate,cyclohexylisocyanate, dimethylphenyl isocyanate, butylisocyanate, andnaphthyl isocyanate are useful.

Diisocyanate substances may be partially reacted with aliphaticcompounds, alicyclic compounds, or aromatic compounds having a hydroxylgroup, an imino group, an amino group, a carboxyl group, a mercaptogroup, an epoxy group, and the like.

In the condensation reaction accompanied by decarboxylation of adiisocyanate compound, a carbodiimidization catalyst can be used. Usableas such a catalyst are, for example, phospholene oxides such as1-phenyl-2-phospholene-1-oxide, 3-methyl-2-phospholene-1-oxide,1-ethyl-2-phospholene-1-oxide, and 3-phospholene isomers thereof.

In order to convert a carbodiimide group-containing polymer into anaqueous polymer, a hydrophilic segment is provided in the molecularstructure of the carbodiimide group-containing polymer. For example, anaqueous polymer containing a carbodiimide group can be obtained byproviding a hydrophilic segment having a functional group which hasreactivity with an isocyanate group. Usable as the hydrophilic segmentare: quaternary ammonium salts of dialkylamino alkylamine (e.g.,quaternary ammonium salts of 2-dimethylaminoethanol); quaternary saltsof dialkylamino alkylamine (e.g., 3-dimethylamino-n-propylamine); alkylsulfonic acid salts having at least one reactive hydroxyl group (e.g.,sodiumhydroxypropanesulfonate); a mixture of polyethylene oxide orpolyethylene oxide, whose terminal is capped with an alkoxy group, and apolypropylene oxide (e.g., polyethylene oxide whose terminal position iscapped with a methoxygroup or an ethoxy group)

As an aqueous cross-linking agent containing an epoxy group, there areexemplified sorbitol polyglycidyl ether, glycerol triglycidyl ether,polyglycerol polyglycidylether trimethylolpropane triglycidyl ether,poly(ethyleneglycol) diglycidyl ether, poly(propyleneglycol) diglycidylether, phenol ethyleneoxide glycidyl ether, and lauryl alcoholethyleneoxide glycidyl ether or the like. In addition to the above,mentioned as examples are: a water-soluble epoxy resin obtained byreacting a carboxy compound, which is obtained through a reactionbetween a polyoxyethylene polyol compound and an acid anhydridecompound, and an epoxy resin having two or more epoxy groups in itsmolecules; and a self-emulsifiable epoxy resin composition obtained bymixing the water-soluble epoxy resin and the epoxy resin having two ormore epoxy groups in its molecules. Such resins can be obtained forexample under the tradenames of XZ 92533.00, XZ 92598.00 and XZ 92446.00from The Dow Chemical Company, Midland, Mich. Examples of the anhydridecompound include, but not particularly limited to, preferably aromaticanhydrides such as phthalic anhydride, trimellitic anhydride, andpyromellitic anhydride; and cyclic aliphatic anhydrides such as maleicanhydride, succinic anhdyride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, alkenyl succinicanhdyride, hexahydrophthalic anhydride, and methyl hexahydrophthalicanhydride. There is no limitation on the epoxy resin having two or moreepoxy groups in its molecules, and all known epoxy resins with an epoxyfunctionality of greater or equal to two can be used. Examples arepolyglycidyl ether obtained from epichlorohydrin and a polyhydriccompound such as, phenol novolac, and cresol novolac bisphenol A,bisphenol F, bisphenol S, resorcinol, hydroquinone or catechin; alkyleneoxide-added bisphenol A; polyalcohols such as polypropylene glycol,1,6-hexanediol, trimethylol propane, glycerin, cyclohexanedimethanol;and polyglycidyl ester and polyglycidyl amine of polycarboxylic acidssuch as adipic acid, phthalic acid, dimer acid and the like.

Aqueous cross-linking agent containing an isocyanate group are, forexample: polyisocyanate mainly containing at least one member selectedfrom the group consisting of an isocyanurate group-containingpolyisocyanate, an urethodione group-containing polyisocyanate, anurethodione group/isocyanurate group containing polyisocyanate, anurethane group containing polyisocyanate, an allophanate groupcontaining polyisocyanate, a biuret group containing polyisocyanate, acarbodiimide group containing polyisocyanate, and an uretodione groupcontaining polyisocyanate, each of which contains 1,6-hexamethylenediisocyanate and/or isophorone diisocyanate as a raw material; and aself-emulsifiable polyisocyanate obtained by reacting a hydrophilicsurfactant having at least one active hydrogen group which can reactwith an isocyanate group or polyethylene ether alcohol containing atleast three poly-ethylene oxide units with fatty acid ester in which thesum of the number of carbons of fatty acid and a hydroxyl containingcompound as raw materials is 8 or more and which has at least one activehydrogen group which can react with an isocyanate group. In addition tothe above, an urethane group-containing polyisocyanate obtained byreaction between 1,6-hexamethylenediisocyanate and/or an isophoronediisocyanate and an active hydrogen group-containing compound orpolyisocyanate obtained by an allophanatization reaction,carbodiimidization reaction, uretodionization reaction, andbiuretization reaction of these diisocyanate compounds can be mentioned.

Examples of suitable crosslinking agents derived from aldehyde arewater-dispersed or water-dispersible or water-soluble phenolformaldehyde resins, amino formaldehyde resins or combinations thereof.

Phenol formaldehyde crosslinking agents include, but are not limited to,reaction products of aldehydes with phenols. Preferred aldehdydes butnot exclusive are formaldehyde and acetaldehyde. A large variety ofphenols can be used such as but not exclusive phenol, cresol,p-phenylphenol, p-tert-butylphenol, p-tert-amylphenol,cyclopentylphenol, cresylic acid, bisphenol-A, bisphenol-F and the likeand combinations thereof. Also acid functional phenols could be used inmaking phenol formaldehyde resins. The crosslinkers can be unetherifiedor etherified with alcohols or polyols. These phenol formaldehyde resinsmay be soluble or self-emulsifiable in water or can be stabilized by useof colloid stabilizers such as polyvinyl alcohol.

Amino formaldehyde crosslinking agents include, but are not limited to,reaction products of aldehydes with amino or amido group containingmolecules. Exemplary aldehydes include, but are not limited to,formaldehyde and acetaldehyde. A large variety of amino or amido groupcontaining molecules can be used such as but not exclusive urea,melamine, benzoguanamine, acetoguanamine, glycoluril and the like.Suitable amino crosslinking resins include melamine-formaldehyde,urea-formaldehyde, benzoguanamine-formaldehyde,acetoguanamine-formaldehyde, glycoluril-formaldehyde resins. Also themethylol groups of an amino formaldehyde resin can be partially or fullyetherified with at least one of the groups of monohydric aliphaticalcohols such as methanol and/or n-butanol. These amino formaldehyderesins may be soluble or self-emulsifiable in water or can be stabilizedby use of colloid stabilizers such as polyvinyl alcohol can be used tostabilize the amino formaldehyde dispersions.

Commercially available amino-formaldehyde resins which are water solubleor water dispersible and useful for the instant purpose include Cymel™301, Cymel™ 303, Cymel™ 370, and Cymel™ 373 (all being products of CytecSurface Specialties, Brussels, Belgium). Other aldehydes used to reactwith the amino compound to form the resinous material are crotonicaldehyde, acrolein, or compounds which generate aldehydes, such ashexamethylene-tetramine, paraldehyde, and the like.

Another class of crosslinking agents for carboxylic acid groups arewater-soluble hydroxyalkylamide crosslinkers such asBis(N,N′-dihydroxyethyl)adipamide and the like. Such compounds arecommercially available under the tradename of PRIMID™ crosslinker resinsfrom EMS-PRIMID in Switzerland, for example PRIMID™ XL-522, PRIMID™SF-4510 and PRIMID™ QM-1260.

The one or more crosslinking agents may be added to the aqueouspolyolefin dispersion as part of the aqueous dispersion formulationprocess; or in the alternative, the one or more crosslinking agents maybe added to the aqueous polyolefin dispersion post dispersionformulation process; or in another alternative, the one or morecrosslinking agents may be added to the aqueous base blend composition,as further described herein.

Depending on the type of food and/or beverage which is to be containedin a coated container, and on required coating properties it may bebeneficial to combine several crosslinkers or some crosslinkers may bemore suited than others. Some crosslinkers may not be suited for allapplications. Some crosslinkers may require the addition of catalystsfor proper cure.

Crosslinkers will help to build thermoset networks which are indicatedby higher values of MEK Double Rubs compared to an identical formulationnot containing the crosslinker.

Optional Acrylic Emulsion Component

The acrylic emulsion component may comprise from 20 to 70, for examplefrom 40 to 60, or in the alternative from 45 to 60, percent by weight ofacrylic solids, based on the weight of the acrylic emulsion. The acrylicsolids present in the acrylic emulsion have an average weight particlesize diameter in the range of from 75 to 450 nm, for example, from 115to 375, or in the alternative from 150 to 300. The acrylic polymerpresent in the acrylic emulsion component has an acid level in the rangeof from 0.25 to 5, for example from 0.25 to 3, or in the alternativefrom 0.5 to 2.5, or in the alternative from 1 to 2 percent by weight ofacid monomers based on the total weight of the acrylic monomers. Theacrylic polymer present in the acrylic emulsion component has a weightaverage molecular weight in the range of from 200,000 to 5,000,000g/mole, for example from 200,000 to 1,000,000 g/mole, or in thealternative from 200,000 to 750,000 g/mole). The acrylic polymer presentin the acrylic emulsion component has a glass transition temperature(T_(g)) in the range of from 0 to 100° C., for example from 7 to 100°C., or in the alternative from 10 to 80° C., or in the alternative from20 to 65° C. The acrylic emulsion component of the present invention hasa pH in the range of from 7 to 10, for example, from 7 to 9.

In a different embodiment of the invention, the acrylic emulsioncomponent may contain from 0.25 to 5, for example from 0.25 to 3, or inthe alternative from 0.5 to 2.5, or in the alternative from 1 to 2percent by weight based on the total weight of the acrylic monomers,copolymerized ethylenically unsaturated carboxylic acid monomer, suchas, for example, acrylic acid, methacrylic acid, crotonic acid, itaconicacid, fumaric acid, maleic acid, monomethyl itaconate, monomethylfumarate, monobutyl fumarate, and maleic anhydride.

Suitable mono-ethylenically unsaturated acid or diacid monomers mayinclude, for example, (meth)acrylic acid, itaconic acid, monomethylitaconate, (meth)acryloxypropionic acid, aconitic acid, fumaric acid,crotonic acid, maleic acid, anhydrides thereof, e.g. maleic anhydride;monomethyl maleate; monoalkyl itaconates; monoalkyl fumarates, e.g.monomethyl fumarate; 2-acrylamido-2-methylpropane sulfonic acid; vinylsulfonic acid; styrene sulfonic acid; 1-allyloxy-2-hydroxypropanesulfonic acid; alkyl allyl sulfosuccinic acid; sulfoethyl(meth)acrylate; phosphoalkyl (meth)acrylates, such as phosphoethyl(meth)acrylate; phosphodialkyl (meth)acrylates; and allyl phosphate.Preferred acid monomers are (meth)acrylic acid, itaconic acid, fumaricacid and maleic acid.

In yet another embodiment of the invention, the acrylic emulsioncomponent may contain up to 5 percent by weight based on the totalweight of the acrylic monomers, copolymerized multi-ethylenicallyunsaturated monomers such as, for example, allyl methacrylate, diallylphthalate, 1,4-butylene glycol dimethacrylate, 1,2-ethylene glycoldimethacrylate, 1,6-hexanediol diacrylate, and divinyl benzene.

In one embodiment, the acrylic emulsion polymer, e.g. homopolymer orcopolymer, can be prepared, for example, by charging, at once orgradually, the monomeric ingredients, water and a surfactant (whenemployed) into a reaction vessel, purging the vessel with an inert gas,such as, for example, nitrogen and heating the vessel to a reactiontemperature in the range of from 50 to 100° C. When the reaction vesselreaches the desired reaction temperature, one or more initiators areadded to the reaction vessel. The reaction is continued for a period oftime sufficient to complete the polymerization process, for example, aperiod in the range of from 1 to 4 hours. Upon near completion or thecompletion of the reaction, the reactor vessel and reaction contentcontained therein are cooled. This synthesis yields an aqueous polymericcomposition comprising the polymer, e.g. homopolymer or copolymer, inwater. In some instances, the composition has the appearance of a milkyemulsion, while in other instances it looks like a clear or hazysolution.

The process for production of the copolymer may include the use of aseed which may be a (meth)acrylate, polystyrene or other seed useful tocontrol the particle size of the emulsion. As is well known in the art,the regulation of initial seed can be used to control the ultimate rangeof particle sizes in the copolymer produced.

As used herein, the term “(meth)acrylate” means acrylate, methacrylate,and mixtures thereof and the term “(meth)acrylic” used herein meansacrylic, methacrylic, and mixtures thereof.

Suitable mono-ethylenically unsaturated monomers may include nonionicmonomers such as, for example, (meth)acrylic ester monomers including,for example, C₁ to C₃₀ (cyclo)alkyl (meth)acrylates, such as, forexample methyl (meth)acrylate, ethyl methacrylate, butyl (meth)acrylate,2-ethylhexyl (meth)acrylate, decyl acrylate, lauryl (meth)acrylate,isodecyl (meth)acrylate; (meth)acrylamide, substituted(meth)acrylamides, such as N-alkyl (meth)acrylamides and N,N-dialkyl(meth)acrylamides; ethylene; propylene; styrene and substitutedstyrenes; butadiene; vinyl esters, such as vinyl acetate and vinylbutyrate; vinyl chloride, vinyl toluene, and vinyl benzophenone;(meth)acrylonitrile; and vinylidene halides, such as, vinylidenechloride. Suitable ionic and hydrophilic mono-ethylenically unsaturatedmonomers may include, for example, hydroxyalkyl (meth)acrylates;glycidyl (meth)acrylate; mono-ethylenically unsaturated acid monomers;acetoacetoxyethyl (meth)acrylate, acetoacetoxyalkyl (meth)acrylates;amine-group containing monomers, such as vinyl imidazole,2-(3-oxazolidinyl)ethyl (meth)acrylate and amine-functional(meth)acrylates, such as tert-butylaminoethyl (meth)acrylate,N,N-dimethylaminoethyl (meth)acrylate and N,N-dimethylaminopropyl(meth)acrylate; N-vinyl pyrrolidone; sodium vinyl sulfonate;phosphoethyl (meth)acrylate; acrylamido propane sulfonate; diacetoneacrylamide; ethyleneureido-functional monomers; isocyanatoalkyl(meth)acrylate, and allyl acetoacetate.

Anionic, nonionic, and amphoteric surfact active agents, that is,surfactants, can be employed in the copolymer synthesis process.

The acrylic emulsion may be polymerized via free radical polymerization,including, for example, thermal, redox (using redox catalysts),photochemical, and electrochemical initiation. Suitable free radicalinitiators or oxidants may include, for example, persulfates, such as,for example, ammonium and/or alkali metal persulfates; peroxides, suchas, for example, sodium or potassium hydroperoxide, t-alkyl peroxides,t-alkyl hydroperoxides, dicumyl hydroperoxide; or t-alkyl peresters,wherein the t-alkylgroup includes at least 5 carbon atoms; perboricacids and their salts, such as, for example, sodium perborate;perphosphoric acids and salts thereof; potassium permanganate; andammonium or alkali metal salts of peroxydisulfuric acid. Such initiatorsmay be used in amounts ranging from 0.01 to 3.0 weight percent, based onthe total weight of monomers.

Suitable redox catalysts comprise one or more oxidant with a suitablereductant. Suitable reductants may include, for example, sodiumsulfoxylate formaldehyde; (iso)ascorbic acid; alkali metal and ammoniumsalts of sulfur-containing acids, such as sodium (bi)sulfite,thiosulfate, hydrosulfite, (hydro)sulfide or dithionite;formadinesulfinic acid; hydroxymethanesulfonic acid; sodium2-hydroxy-2-sulfinatoacetic acid; acetone bisulfate; amines, such asethanolamine, glycolic acid; glyoxylic acid hydrate; lactic acid;glyceric acid, malic acid; tartaric acid; and salts of thereof may beused in amounts of from 0.01 to 5.0 weight percent based on the totalweight of monomers.

Redox reaction catalyzing metal salts of iron, copper, manganese,silver, platinum, vanadium, nickel, chromium, palladium, or cobalt maybe added for the formation of such polymers. Typical levels of catalyticmetal salts used is in the range of from 0.01 ppm to 25 ppm, and mayrange up to 1.0 wt. %, based on the total weight of monomers. Mixturesof two or more catalytic metal salts may also be usefully employed.Chelating ligands, which can be used with catalytic metal salts, includemultidentate aminocarboxylate ligands, such as, for example,nitrilotriacetic acid (NTA, a tetradentate ligand), ethylene diaminediacetic acid (EDDA, a tetradentate ligand), N-(hydroxyethyl) ethylenediamine triacetic acid (HEDTA, a pentadentate ligand), and ethylenediamine tetraacetic acid (EDTA, a hexadentate ligand).

Any monomer in any polymerization may be added neat, i.e., not as anemulsion in water, or as an emulsion in water. The monomer may be addedin one or more additions or continuously, linearly or not, over thereaction period, or combinations thereof. Suitable surfactants includecationic, anionic, and non-ionic surfactants. Anionically stabilizedemulsion polymers may be stabilized by anionic surfactant or a mixturethereof with one on more nonionic surfactant. Conventional surfactantsmay be used to stabilize the emulsion polymerization systems before,during, and after polymerization of monomers. These conventionalsurfactants will usually be present at levels of 0.1 percent to 6percent by weight based on the total weight of monomer inpolymerization. At least one anionic, nonionic, or amphoteric surfactantmay be used, or mixtures thereof. Examples of anionic emulsifiersinclude sodium lauryl sulfate, sodium dodecyl benzene sulfonate,dioctylsulfosuccinate, sodium polyoxyethylene lauryl ether sulfate,sodium dodecyl diphenyloxide disulfonate and other diphenylsulfonatederivatives, and sodium salt oftert-octylphenoxyethoxypoly(39)ethoxyethyl sulfate. Surfactants in thefree acid form and in the salt form with other counterions may also beused, for example dodecylbenzene sulfonic acid and dodecylbenzenesulfonic acid ammonium salt.

In one embodiment, the acrylic emulsion can be a single stage ormultistage polymer. The polymerization techniques used for preparing themultistage acrylic polymer present in the acrylic emulsion, alsoreferred to as hard-soft polymer particles with one component having alower Tg (soft) relative to the other component having a higher Tg(hard), where one component is polymerized in the presence of the otherare well known in the art. The hard-soft polymer particles are typicallyprepared by a multistage aqueous emulsion polymerization process, inwhich at least two stages differing in composition are polymerized in asequential fashion. Multi-stage polymerization techniques suitable forpreparing the hard-soft polymer particles are disclosed, for example, inU.S. Pat. Nos. 4,325,856, 4,654,397, and 4,814,373. In the multistagepolymerization process to prepare the hard-soft polymer, either the softpolymer or the hard polymer is prepared as a dispersion of the firstpolymer particle in water, followed by the polymerization of the otherpolymer (the hard polymer or the soft polymer, respectively) in thepresence of the first polymer particles to provide the hard-softparticles.

The acrylic emulsion could also be a blend of two or more acrylicemulsions with different Tgs, wherein the difference between the two ormore Tgs is at least 10° C.

As used herein, unless otherwise indicated, the term “average particlesize,” (for acrylic emulsion) with regard to the acrylic emulsion andcomponents thereof, means the particle size as determined by lightscattering (LS) using a BI-90 particle size analyzer, BrookhavenInstruments Corp. (Holtsville, N.Y.).

As used herein, unless otherwise indicated, the phrase “molecularweight” (for acrylic emulsions) refers to the weight average molecularweight as measured by gel permeation chromatography (GPC) against apolymethylmethacrylate (PMMA) or polystyrene (PS) standard.

As used herein, unless otherwise indicated, the term “Tg” or “glasstransition temperature” of a polymer, with regard to the acrylicemulsion and components thereof, refers to the Tg of a polymercalculated by using the Fox equation (T. G. Fox, Bull. Am. Physics Soc.,Volume 1, Issue No. 3, page 123 (1956), i.e.

$\frac{1}{Tg} = {\frac{w_{1}}{{Tg}_{(1)}} + \frac{w_{2}}{{Tg}_{(2)}}}$

For a copolymer, w₁ and w₂ refer to the weight fraction of the twocomonomers and Tg₍₁₎ and Tg₍₂₎ refer to the glass transition temperatureof the two corresponding homopolymers. The Tg of various homopolymersmay be found, for example, in Polymer Handbook, edited by J. Brandrupand E. H. Immergut, Interscience Publishers. The “Experimental Tg” of apolymer, with regard to the acrylic emulsion and components thereof, ismeasured by differential scanning calorimetry (DSC) using the mid-pointin the heat flow versus temperature transition as the Tg value. Atypical heating rate for the DSC measurement is 20° C./minute.

Forming the Aqueous Based Blend Composition

The various aqueous polyolefin dispersion components, as describedabove, are blended together via various means, for example, mixers suchstatic mixers, also known as in-line mixers, or an agitated tank to formthe aqueous based blend composition. The aqueous based blend compositioncan be further formulated into a coating composition by adding one ormore coating formulation components such as one or more solvents, one ormore catalysts, one or more antioxidants, one or more lubricants, andone or more additional coating formulation components, and combinationsthereof. The one or more coating formulation components may be added tothe aqueous based blend composition after the aqueous based blendcomposition is prepared, or in the alternative, the one or more coatingformulation components may be added during the preparation of theaqueous based blend composition or components thereof, i.e. the aqueouspolyolefin dispersion.

Coating Applications and Forming Coated Containers or Closure Devices

The aqueous based blend compositions of the present invention may beused, for example, in container, e.g. can, coating applications, orclosure device coating applications. Such coated container devicesinclude, but are not limited to, cans such as beverage cans, food cans;aerosol containers such as those for non-food products, e.g. hair spray,hair dye, or color spray lacquers; drums; kegs; pails; decorative tins;open trays; tubes; bottles; monoblocs; and the like. The coated closuredevices include, but are not limited to, caps, lids such as thinaluminum foil based lids for yogurt and butter containers, or crowncorks; closures for glass jars and bottles such as roll-on closures,vacuum closures, pilfer-proof closures, easy peel lids for can closures,and easy open end or conventional ends for cans. Cans may be 2 piececans or 3 piece cans. Beverage cans include, but are not limited to,beer cans, carbonated soft drink cans, energy drink cans, isotonic drinkcans, water cans, juice cans, tea cans, coffee cans, milk cans, and thelike. Food cans, include, but are not limited to, vegetable cans, fruitcans, meat cans, soup cans, ready meal cans, fish cans, edible oil cans,sauce cans and the like. Such cans may have any shapes; for example,such can may have a cylindrical shape, cubical, spherical,semi-spherical, bottle shape, elongated cubical shape, shallow or tallshape, round or rectangular shape or any other suitable shape. Thecoated container devices according to the instant invention may beformed via any conventional method. For example, the coated containerdevice may be formed via stamping, drawing, redrawing, wall ironing,bending, beading, embossing, debossing, flanging, necking, stretching,blow-stretching and any other suitable conventional method. Such methodsare generally known to those having ordinary skill in the art. Theaqueous based blend compositions may, for example, be applied to a metalsubstrate, e.g. metal sheet or metal foil, and then the coated substratemay be formed into a coated container device or a coated closure device.In the alternative, the metal substrate may be formed into a containerdevice or a closure device, and then the container device or the closuredevice is coated with one or more aqueous based blend compositions toform the coated container device or coated closure device. The coatingmay be applied via any method; for example, via roller coating, spraycoating, powder coating, dip coating, electrodeposition coating,printing, wash coating, flow coating, and/or curtain coating.

The one or more aqueous based blend compositions applied to the at leastone surface of the metal substrate may be dried via any conventionaldrying method. Such conventional drying methods include but, are notlimited to, air drying, convection oven drying, hot air drying, and/orinfrared oven drying. During the drying process, crosslinking of one ormore base polymers, stabilizing agents, or combinations thereof,involving the one or more crosslinking agents, may occur. Additionalcure might occur by radiation cure, e.g. electron-beam cure. The one ormore aqueous based blend compositions applied to the at least onesurface of the metal substrate may be dried at any temperature. The oneor more aqueous based blend compositions applied to the at least onesurface of the metal substrate may be dried at a temperature in therange of about 60° F. (15.5° C.) to about 700° F. (371° C.) for a periodof less than about 40 minutes, for example, less than 20 minutes, orless than 10 minutes, or less than 5 minutes, or less than 2 minutes, orless than 1 minute, or less than 20 seconds. All individual values andsubranges from about 60° F. (15.5° C.) to about 700° F. (371° C.) areincluded herein and disclosed herein; for example, the one or moreaqueous based blend compositions applied to the at least one surface ofthe metal substrate may be dried at a temperature in the range of about60° F. (15.5° C.) to about 500° F. (260° C.) for a period of less thanabout 40 minutes, for example, less than 20 minutes, or less than 10minutes, or less than 5 minutes, or less than 2 minutes, or less than 1minute, or in the alternative, the one or more aqueous based blendcompositions applied to the at least one surface of the metal substratemay be dried at a temperature in the range of about 60° F. (15.5° C.) toabout 450° F. (232.2° C.) for a period of less than about 40 minutes,for example, less than 20 minutes, or less than 10 minutes, or less than5 minutes, or less than 2 minutes, or less than 1 minute.

The coated metal substrate may further be coated with one or moreconventional coating compositions, or it may further be laminated to oneor more other layers. Such conventional coating compositions aregenerally known to person of ordinary skill in the art, and they mayinclude, but are not limited to, epoxy resin coating compositions,acrylate based coating compositions, and polyester based coatingcompositions. The lamination process is generally known, and exemplarylamination layers may include, but are not limited to, polyesterlaminates, polyolefin based laminates such as polypropylene laminates.

The one or more aqueous based blend compositions applied to at least onesurface of a metal substrate may have a cross cut adhesion rating of atleast 3B; for example, 5B, measured according to ASTM-D 3359-08. The oneor more aqueous based blend compositions applied to at least one surfaceof a metal substrate may have a methyl ethyl ketone (MEK) double rubrating of at least 10. The one or more aqueous based blend compositionsapplied to at least one surface of a metal substrate may have a wedgebend pass rating of at least 90 percent, measured via a Gardner“COVERALL” Bend Tester IG 1125.

EXAMPLES

The following examples illustrate the present invention but are notintended to limit the scope of the invention.

Preparation of Aqueous Polyolefin Dispersion A (POD A)

Aqueous polyolefin dispersion A (POD A) was prepared according to thefollowing procedures based on the formulation components listed inTable 1. PP 6D43, polypropylene having a melt index of approximately inthe range of 32 to 38 g/10 minutes (ASTM D 1238, 230° C./2.16 Kg),available from The Dow Chemical Company, as the base polymer, andPRIMACOR™ 5980i (CAS No. 9010-77-9), ethylene acrylic-acid copolymerhaving acrylic acid content of approximately in the range of 19.5 to21.5 weight percent and a melt index of approximately 300 g/10 minutes(ASTM D 1238, 190° C./2.16 Kg), available from The Dow Chemical Company,as a first stabilizing agent, and Licocene 6452 maleic anhydride graftedpolypropylene having a softening point of approximately 130 to 150° C.,available from Clariant Corporation, as a second stabilizing agent, werefed into a 25 mm diameter twin screw extruder by means of a controlledrate feeder where they were forwarded and melted. The extrudertemperature profile was ramped up to approximately 160° C. prior to theaddition of the initial water and DMEA, dimethylethanolamine (CAS No.108-01-0), as the neutralizing agent, and subsequently, it was cooledback down to a temperature below 100° C. by the end of the extruderafter the dilution water was added. The extruder speed was approximately1200 rpm Amine neutralizing agent and water were mixed together and fedto the extruder at the initial water introduction point. The dilutionwater was fed via a second pump, and it was introduced into the dilutionzone of the extruder. The initial water and dilution water streams wereoptionally preheated to the extruder temperature. At the extruderoutlet, a back-pressure regulator was used to adjust to a suitablepressure inside the extruder barrel to reduce steam formation at theoperating temperature. The resulting dispersions were cooled andfiltered through a 200 micron filter.

TABLE 1 Average Second Initial Dilution Particle First StabilizingNeutralizing Water Water Size Aqueous Base Polymer Stabilizing AgentAgent Rate Rate Diameter Dispersion (g/min) Agent (g/min) (g/min)(ml/min) (ml/min) (ml/min) (microns) POD A 6D43 PRIMACOR ™ LICOCENE ™DMEA 70 240 1.0 polypropylene 5980i 6452 (23) (31) (212) (68)Preparation of Coating Compositions 1-11

Crosslinkers (i.e. Primid QM1260 or Phenolic GPRI 4003) were added toaqueous polyolefin dispersion A (“POD A”) under mixing on a lab mixer atmedium shear to form aqueous dispersion blends 1-11. After mixing theaqueous based blend compositions 1-11 for approximately 5 minutes, basic(pH 9-10) water followed by a solvent blend of butanol/butyl cellosolve(1:1 ratio) was added slowly to the aqueous based blend compositions1-11 under medium shear. An amine neutralized dodecylbenzene sulfonicacid (DDBSA) catalyst (Nature 5925) was used with the phenolic resin andwas added under medium shear at this point, and further mixed forapproximately 5 additional minutes. The solvent blend also containedIrganox™ 1010, an antioxidant used to protect the polyolefin dispersionat high cure temperatures. All of the mixing was completed in a 4 oz.wide mouth glass jar using a Teflon paddle blade stirrer. Basic waterincluded 787 g deionized water and 2.36 g dimethylethanolamine (DMEA),and a pH of approximately 9-10. The solvent blend included 152 gbutanol, 152 g butyl cellosolve, and 0.14 g Irganox 1010. CoatingComposition formulation components are reported in Table 2 (CoatingsFormulations with Primid QM 1260) and 3 (Coatings Formulations withPhenolic Resin GPRI 4003).

TABLE 2 Solvent Total POD Primid Water Blend Formulation Total CoatingAmount Primid:Acid Amount Amount Amount Amount Formulaion SampleCompostion (g) ratio (g) (g) (g) (g) % Solids Appearance 1 25.00 1:10.72 25.79 8.96 60.47 20 Homogeneous 2 25.00 0.75:1.0  0.54 25.79 8.9660.29 20 Homogeneous 3 25.00 0.5:1.0 0.36 25.79 8.96 60.11 20Homogeneous 4 25.00 0.25:1.0  0.18 25.79 8.96 59.93 20 Homogeneous 525.00 0.2:1.0 0.14 25.79 8.96 59.89 20 Homogeneous 6 25.00 0.1:1.0 0.0725.79 8.96 59.82 20 Homogeneous 7 50.00 0.05:1.0  0.07 51.58 17.93119.57 20 Homogeneous 8 15.00 None 0.00 15.47 5.38 35.85 20 Homogeneous

TABLE 3 GPRI 4003 level GPRI Nacure Solvent POD (based 4003 5925 WaterBlend Total Total Coating Amount on Amount Amount Amount AmountFormulation Formulaion Sample Formulation (g) solids) (g) (g) (g) (g)Amount (g) % Solids Appearance 9 17.50 30% 7.56 0.06 25.72 8.96 59.81 20Significant settling 10 20.00 20% 5.04 0.06 25.75 8.96 59.81 20 Slightsettling 11 22.50 10% 2.52 0.06 25.77 8.96 59.81 20 Slight settlingCoating Application

Aluminum panels (can stock clean aluminum measuring 0.009×4″×12″ fromAll Foils), were cleaned with acetone, and then dried. About 3 grams ofeach inventive coating formulations 1-11 was applied individually to thealuminum panel via a 3.6 mil #36 wirewound drawdown bar thereby coatingone surface of the aluminum panel. Coating application was completedapproximately one hour after respective coating composition 1-11 wasprepared. Subsequently, the panel was placed into a convection oven on amass of solid aluminum plate to be cured for 130 seconds at 400° F. Thecoated aluminum panels were tested for coating thickness, cross cutadhesion before sterilization (retort), cross cut adhesion and blushafter sterilization (retort) according to the procedures describedbelow. The results are reported in Tables 4.

TABLE 4 Coating Appearance Wet Adhesion Coating Wet Adhesion Coating(blush after (after lactic Appearance (after water Coating Thickness Drylactic acid acid retort 30 min (blush after retort 30 min FormulationNotes (microns) Adhesion retort) @ 121° C.) water retort) @ 129° C.) 11:1 Primid 12.0 5B 5 3B 5 5B 2 0.75:1 12.5 5B 5 4B 5 5B Primid 3 0.5:1.011.2 5B 5 5B 5 5B Primid 4 0.25:1 10.8 5B 5 5B 5 5B Primid 5 0.2:1 10.05B 5 5B 5 5B Primid 6 0.1:1 11.8 5B 4 5B 4 3B Primid 7 0.05:1 10.5 4B 53B 3 0B Primid 8 POD only 11.3 5B 4 0B 4 0B 9 30% 10.3 5B 5 4B 5 4Bphenolic 10 20% 10.2 5B 5 5B 5 5B phenolic 11 10% 9.6 5B 5 5B 5 3Bphenolic

Test Methods

Test methods include the following:

Cross-Cut Adhesion Before Retort (Dry Adhesion)

Cross-cut adhesion is measured according to ASTM-D 3359-02, Measuringadhesion by tape test, Method B., using a fresh snap off razor blade anda stainless steel template to score eleven lines. This method providesthe procedure for assessing the adhesion of coating films to metallicsubstrates by applying and removing a tape (grade: 3M 410M double coatedpaper tape) over the cuts made in the film. Place the center of a pieceof tape over the grid and in the area of the grid smooth into place by afinger. To ensure good contact with the film rub the tape firmly with atongue depressor. Within 90±30 seconds of application, remove the tapeby seizing the free end and rapidly (not jerked) pulling it off at asclose to an angle of 180 degrees as possible. Inspect the grid area forremoval of coating from the substrate using the illuminated magnifier.Rate the adhesion in accordance with the scale in table A.

Cross Cut Adhesion After Retort (Wet Adhesion)

In addition to testing cross cut adhesion on the dry panels prior towater retort exposure, a cross-cut adhesion test is performed within anhour of being removed from the autoclave and rated for adhesion asdescribed in the cross cut adhesion section. The adhesion is rated inaccordance with the scale given in table A.

TABLE A Cross-cut Adhesion Rating Scale 5B The edges of the cuts arecompletely smooth; none of the squares of the lattice is detached. 4BSmall flakes of the coating are detached at intersections; less than 5%of the area is affected. 3B Small flakes of the coating are detachedalong the edges and at intersections of cuts. The area affected is 5-15%of the lattice. 2B The coating has flaked along the edges and on partsof the squares. The area affected is 15-35% of the lattice. 1B Thecoating has flaked along the edges of cuts in large ribbons and wholesquares have detached. The area affected is 35-65% of the lattice. 0BFlaking and detachment is worse than 1BRetort Resistance (Water)

The coated panels were immersed in water in individual pressurizableglass beakers that were contained in a secondary container tray, andplaced into a Tuttnauer 10″ dia×18″ Deep Chamber Autoclave model 1Z-TUT-EZ-10 where they were retorted at 129° C. for 30 minutes. Thepanels were removed, rinsed with water, and dried. The coatingappearance was then rated on a scale of 1-5 (5—best, 1—worst) asdetermined by blush (a whitish appearance of the coating) as shown intable B.

Retort Resistance (Lactic Acid)

The coated panels were immersed in 2% lactic acid in individualpressurizable glass beakers that were contained in a secondary containertray, and placed into a Tuttnauer 10″ dia×18″ Deep Chamber Autoclavemodel 1 Z-TUT-EZ-10 where they were retorted at 121° C. for 30 minutes.The panels were removed, rinsed with water, and dried. The coatingappearance was then rated on a scale of 1-5 (5—best, 1—worst) asdetermined by blush (a whitish appearance of the coating) as shown intable B.

TABLE B Coating Appearance after Retort Rating Scale 5 No Blush 4 VerySlight blush 3 Slight blush 2 Blush 1 Strong BlushCoating Thickness

Coating thickness was measured according to ASTM-D 1186-93,Non-destructive measurement of dry film thickness of non magneticcoatings applied to a non-ferrous base, using a Byko-Test 8500 coatingthickness gauge. The standard aluminum panel without any coating wasused for calibration. The thickness of the coating of the coated panelswas reported as the range of 10 measurements, wherein each measurementof the thickness of the coating of the coated panels was measured usinga probe for non-ferrous materials relative to the thickness of thecoating of the standard panel, i.e. zero. The measured thickness wasreported in microns.

The present invention may be embodied in other forms without departingfrom the spirit and the essential attributes thereof, and, accordingly,reference should be made to the appended claims, rather than to theforegoing specification, as indicating the scope of the invention.

We claim:
 1. An aqueous based blend composition comprising: an aqueouspolyolefin dispersion comprising the melt blending product of one ormore base polymers comprising one or more polyolefins and one or morestabilizing agents in the presence of water and optionally one or moreneutralizing agents, wherein the polyolefin dispersion has an averagevolume particle size diameter in the range of from 400 to 1500 nm, and apH range from 8 to 11; and one or more crosslinking agents selected fromthe group consisting of phenol-formaldehyde resins, hydroxyalkylamideresins, amino-formaldehyde resins; epoxy group containing resins, andcombinations thereof, wherein said crosslinking agents comprise from 0.1to 50 percent by weight based on the solid content of the dispersion; anacrylic emulsion comprising two or more acrylic emulsions with differentglass transition temperatures wherein the difference between the two ormore glass transition temperatures is at least 10° C.; and wherein saidaqueous based blend composition has a solid content in the range of from15 to 70 percent by weight of solids, based on the weight of the aqueousbased blend composition, wherein said solid content of said blendcomposition comprises up to 99.9 percent by weight of the one or morebase polymers, based on the weight of the solid content of the aqueousbased blend composition, and a pH in the range of from 8 to
 11. 2. Afilm obtained from the aqueous based blend composition of claim
 1. 3.The film of claim 2, wherein said film has a thickness in the range offrom 1 to 20 μm.
 4. A multilayer film comprising one or more filmsaccording to claim
 2. 5. A container device comprising a substrate andthe film of claim 2 associated with at least one surface of saidsubstrate.
 6. The aqueous based blend composition of claim 1, whereinsaid crosslinking agent is hydroxylalkylamide.
 7. The aqueous basedblend composition of claim 1, further comprising one or more bindercompositions selected from the group consisting of acrylic latex, vinylacrylic latex, styrene acrylic latex, and any combination thereof.
 8. Aprocess for producing an aqueous based blend composition comprising:selecting an aqueous polyolefin dispersion comprising the melt blendingproduct of one or more base polymers comprising one or more polyolefinsand one or more stabilizing agents in the presence of water andoptionally one or more neutralizing agents, wherein the polyolefindispersion has an average volume particle size diameter in the range offrom 400 to 1500 nm, and a pH range from 8 to 11; and selecting one ormore crosslinking agents selected from the group consisting ofphenol-formaldehyde resins, hydroxyalkylamide resins, amino-formaldehyderesins; epoxy group containing resins, and combinations thereof, whereinsaid crosslinking agents comprise from 0.1 to 50 percent by weight basedon the solid content of the dispersion; selecting an acrylic emulsioncomprising two or more acrylic emulsions with different glass transitiontemperatures wherein the difference between the two or more glasstransition temperatures is at least 10° C.; contacting said aqueouspolyolefin dispersion and said one or more crosslinking agents and saidacrylic emulsion to produce said aqueous based blend composition;wherein said aqueous based blend composition has a solid content in therange of from 15 to 70 percent by weight of solids, based on the weightof the aqueous based blend composition, wherein said solid content ofsaid blend composition comprises up to 99.9 percent by weight of the oneor more base polymers, based on the weight of the solid content of theaqueous based blend composition and a pH in the range of from 8 to 11.